Method of making halogens.



COULTER w. JONES AND ARTHUR n. SCHAEFER, or MIDLAND, MICHIGAN, assrenons TO THE DOW CHEMICAL COMPANY, or MIDLAND, MICHIGAN, A conroaarron or I 1 TE I W T1 @FFICB MICHIGAN.

METHOD OF MAKING HALOGENS.

1,036,12L Specification of Letters Patent.

No Drawing.

To all whom it may concern:

Be it known that we, -COULTER W. Jones and ARTHUR E, SCHAEFER, citizens of the United States, and residents of Midland, county of Midland, and State of Michigan, have jointly invented a new.'and useful Improvement in Methods of Making Halogens, of which the following is aspecification, the principle of the invention beingherein explained and the best mode in which We have 7 contemplated applying that; principle, so as to distinguish it from other inventions.

The present invention, relating, as indicated, to the making of halogens, has more particular regard to the making of a halogen from a metallic haloid while simultaneously producing a haloid from the corresponding trioxygen salt. Stated more specifically, it is proposed to make chlorin, bromin or iodin from a metallic chlorid, bromid, or iodid by treatment with a chlorate, bromate or iodate preferably of an alkali or alkaline earth, whereby the corresponding chlorid, bromid or iodid is simultaneously produced.

To the accomplishment of these and related ends, said invention, then, consists of the means and steps hereinafter fully described and particularly pointed out in the claims. I

The present improved process is based on the discovery that when certain metallic haloids are mixed with the tri-oxygen haloid salts of the alkalis or alkaline earths in water solution, the halogen of the metallic haloid is liberated, the metal of the metallic haloid is oxidized and precipitated, and the tri-oxygen salt reduced to haloid. Thus, for instance, when potassium loromate and bro mid of iron are brought together in a water solution, bromin is liberated, ferric oxid precipitated, and potassium bromid formed. The reaction is quantitative, and by the use of the proper amounts of material practically all of the bromin in the bromid of iron may be liberated, and recovered, the bromate Application filed September 23, 1909. Serial No. 519,244.

reduced to bromid, and the iron precipitated. I

The following reactions indicate the chemistry of the process involved:

, As indicated, these reactions take place without the addition of an acid to the reacting mixture. 7

,It will, of course, be understood that the ferrous salts are first oxidized to ferric before the liberation of the bromin, and the reactions, as written, therefore express th net results.

In the following description, we set forth in detail one approved method of carrying out the invention, such disclosed mode, however, constituting but one of the various ways in which the principle of the invention may be used.

\Ve prefer to mix together cautiously in a suitable closed vessel, practically chemical equivalent weights of bromid of iron liquor and bromate of potash, together with enough water to make a fluid pulp with the result ing precipitate. By applying heat, (most conveniently by the injection of steam) the bromin' liberated by the reaction is driven off or distilled and maybe condensed in i any suitable manner, as by dilution, settling andv decantation, or by filtration. If it be suitable condensers or it maybe used for desired to liberate also the bromin in this bromid, it may ,be conveniently done by the addition of more bromate together with an acid, such as sulfuric acid, by the well known reaction and the liberated bromin may then be distilled off as before.

The original charge may conveniently contain enough bromate for both the reacof nickel and cobalt, may be used in the same manner as above described for bromid of iron, and other bromates such as those of sodium may likewise be used. We write the following reactions Metallic chlorids and iodids, as, for instance, chlorid or iodid of iron, may be used with a chlorate or iodate to produce chlorin or iodin and the corresponding chlorid or iodid. The following reactions will here apply We are familiar with the well known use of'chlorates with acid in the manufacture of bromin from bittern and mother liquors containing combined bromin, but we know of no instance of the use or application of reactions of the class above presented between metallic chlorids, bromids or iodids and chlorates, bromates or iodates for the liberation of the halogen in the metallic salt and for the simultaneous reduction of the,chlorate, bromate or iodate without the use of acids. We are also familiar with the likewise well known method of distilling liberated bromin with heat or direct steam as described above and do not claim that as a part of our invention.

Whileiron is the specific metal, the haloid of which is herein referred to as bein available for use in our. improved met 0d of making halogens, it will be understood of course that the remaining metals of the iron groupv will react-in a similar fashion, and yetother metallic haloids may be found equally good for this purpose. Similarly,

while potassium bromate has been described as the preferred tri-oxygen haloid salt, it will be understood that in place of such p0? tassium bromate the corresponding salts of other members of the alkali or alkaline earth groups of metals may be used. Wherever, accordingly, reference is made in this specification or the following claims to the tri-oxygen haloid salt of an alkali, it is intended to connote by the term alkali, metals of the alkaline earth group as well.

Other modes of applying the principle of our-invention may be employed instead of the one explained, change being made as regards the rocess herein disclosed, provided the steps stated by any one of i the following claims or the equivalent of such stated step or steps be employed.

\Ve therefore particularly point out and distinctly claim as our invention -1. In a method of making 'halogens, the step which consists in treating the haloid of a metal belonging to the iron group with a tri-oxygen haloid salt in a water solution and without the addition of an acid.

2. In a method of makin halogens, the step whichconsists intreatlng the haloid of a metal belonging to the iron group with a tri-oxygen haloid salt of an alkali in a Water solution and without the addition of an acid.

3. In a method of making halogens, the step which consists in treating an iron haloid with a tri-oxygen haloid salt in a water solution and without the addition of an acid.

4. In a method of making halogens, the

step which consists in treating an iron haloid with the tri=oxygen haloid salt of an alkali in a water solution and without the addition of an acid. f

5. The method of producing bromin, which consists in treating the bromid of a metal belonging to the iron group with a tri-oxygen haloid salt'in a water solution and 'without the addition of an acid.

6. The method of producing bromin, which consists in treating the bromid of a metal belon ing to the iron group with a tri-oxygen aloid salt of an alkali -in a water solution and without the addition of an acid.

7. The method of producing bromin,

the tri-oxygen haloid salt of an alkali in a water solution and without the addition of an acid.

10. The method of producing bromin, which consists in treatin a bromate in a water so ution and without the addition of an acid.

11. The method of producing bromin, which consists in treating iron bromid with the bromate of an alkali in a water solution and without the addition of an acid.

iron bromid with 12. The method of making bromin, which consists in treating iron bromid with potassium bromate in a water solution and without the addition of an acid.

Signed by us this 18th day of September,

COULTER W. JONES. ARTHUR E. SGHAEFER. Attested by- LEO W. LOWE, FLORENCE BRODERICK. 

